1. Field of the Invention
This invention relates to a method of forming monolayers, particularly patterned monolayers, of particles in two or more groups of different particle sizes, and to products formed thereby. It is particularly concerned with forming an ordered array of such particles in a monolayer, particularly a patterned monolayer, which may be incorporated into a film. Films formed by the inventive method usually have anisotropic conductive pathways formed by ordered arrays of conductive particles, and are especially useful in interconnection technology in the electronics industry. The invention further relates to a method of forming a film having a monolayer of substantive particles therein, where the particles are in two or more groups of different sizes and particularly where the arrays of particles are arranged in a pattern. When the arrays of particles are arranged in a pattern, the pattern of the particles may be specifically designed according to the end user's requirements.
The invention is also useful in other fields of technology and may be applied to particles, which are not electrically conductive.
2. Brief Description of Related Technology
Anisotropically-conductive adhesives and the ordering of “magnetic holes” in ferrofluids is discussed in International Patent Publication No. WO 95/20820 (“the PCT '820 publication”), the disclosure of which is expressly incorporated herein by reference.
Japanese Patent Document No. JP 62-127 194 of Fujikura Cable Works KK describes the production of anisotropic conductive solder sheets by forming an adhesive coating having a thickness of less than 10 micrometers on a support film, applying soft solder powder having a grain size of 10-50 micrometers onto the adhesive coating, and filling the spaces between granules of the solder with a plastic material. It is stated that the soft solder granules can be evenly dispersed in the plastic material on the film. However, application of particles onto an adhesive film to which the particles adhere on contact is not believed likely to achieve satisfactory dispersion or ordering of the particles in the plane of the film.
European Patent Document No. EP 0 691 660 A1 of Hitachi Chemical Co. Ltd. (“the EP '660 publication”) describes an anisotropically electro-conductive film material produced by adhering electro-conductive particles to an adhering layer formed on a support and fixing the particles therein, and then introducing a film-forming resin incompatible with the adhering material between the electro-conductive particles, the film material having electro-conductivity only in the film thickness direction via the electro-conductive particles uniformly dispersed in the plane direction. The particles may be arranged in a grid or zig zag pattern in the plane by means of a film, net or screen having holes therein (“screen”), through which the particles are fixed on the adhering layer. The particles and the screen may be electrostatically charged with different electric charges. However problems exist in the use of such a screen, including difficulty in producing and handling thin screens, and making the desired patterns of holes. An individual screen would be required for each pattern. Also it would be difficult to (1) ensure that all of the holes are filled by particles and (2) guard against clogging of at least some of the holes by the adhesive material. Removal of the screen may also cause disruption of the pattern. The use of electrostatic charging would be a complex procedure involving large electrical fields.
U.S. Pat. No. 5,221,417 (Basavanhally) describes the use of photo-lithographic masking and etching to form a matrix array of mutually isolated ferromagnetic elements. These elements are magnetized and a single layer of conductive ferromagnetic particles is adhered to an upper surface of each of the ferromagnetic elements, so that the conductive particles are in an array. The layer of particles is then contacted with a layer of soft adhesive polymer to cause penetration of the particles into the polymer. The adhesive polymer is then hardened to assure containment of the particles in the polymer. The adhesive polymer containing the conductive particles is used for interconnecting conductor arrays. However, it is believed that this technique may be used only with conductive particles which are ferromagnetic. Such particles may be difficult to obtain in specific shapes, sizes and types (e.g., monodisperse spheres.)
Japanese Patent Document No. JP 3-95298 discloses a conductive and magnetic fluid composition comprising colloid ferromagnetic particles and conductive particles dispersed in a carrier organic solvent.
U.S. Pat. No. 4,737,112 discloses an anisotropically conductive composite layer medium comprising electrically conductive magnetic particles in a non-conductive matrix. The particles are aligned via the interaction of an applied magnetic field with the electrically conductive particles. The invention relies on the use of magnetic particles as the conductors, and so has no utility in the preparation of ordered arrays of non-magnetic and substantially non-magnetic particles or in the preparation of systems in which ordered arrays are transferred from one substrate to another.
In the PCT '820 publication, a composition is described which includes: (i) a ferrofluid of a colloidal suspension of ferromagnetic particles in a non-magnetic carrier liquid, and (ii) electrically-conductive particles having substantially uniform sizes and shapes, dispersed in the ferrofluid.
The average particle size of the electrically conductive particles is at least 10 times that of the colloidal ferromagnetic particles. The non-magnetic carrier liquid may be curable or non-curable. Examples of the liquid include a curable liquid composition, a mixture of a curable liquid composition and a liquid carrier in which the ferromagnetic particles have been suspended, or a non-curable carrier liquid, provided the electrically-conductive particles have a latent adhesive property.
In the PCT '820 publication, a method of making an anisotropically-conductive bond between two sets of conductors is also described. The method includes applying to one set of conductors a layer of an adhesive composition of the composition so described; bringing a second set of conductors against the layer of adhesive composition; exposing the layer of adhesive composition to a substantially uniform magnetic field such that interaction between the ferrofluid and the electrically-conductive particles causes the electrically-conductive particles to form a regular pattern of particles each in electrical contact with an adjacent particle and/or with a conductor in one or both sets whereby conductive pathways are provided from one set of conductors to the other set, each pathway including one or more of the electrically-conductive particles; and curing the composition to maintain the pattern in position and to bond the conductors.
It may not however always be convenient to install a means for creating a magnetic field at the location of assembly of two sets of conductors. Therefore, in European Patent Document No. EP 757 407 (“the EP '407 publication”), the disclosure of which is incorporated herein by reference, other ways are described of achieving the benefits of the invention of the PCT '820 publication.
The EP '407 publication describes an anisotropically-conductive film or a substrate having a surface coated with an anisotropically-conductive coating. The film or coating is formed by solidifying a composition which includes a solidifiable ferrofluid composition and electrically-conductive particles dispersed in the ferrofluid. The ferrofluid includes a colloidal suspension of ferromagnetic particles in a non-magnetic carrier. The electrically-conductive particles having been arrayed in a non-random pattern by application of a substantially uniform magnetic field to the composition in a liquid state and have been locked in position by solidification of the composition.
The EP '407 publication also describes a solid-form anisotropically-conductive film or a substrate having a surface coated with a solid-form anisotropically-conductive coating the film or coating includes a composition containing colloidal ferromagnetic particles and electrically-conductive particles arrayed in a non-random pattern.
The term “ferromagnetic” as used herein includes ferrimagnetic materials such as ferrites.
The term “solidifiable” as used herein means capable of existing as a solid at ambient temperatures (e.g., temperatures less than about 40° C., usually about 20-30° C.). Solidifiable compositions include curable compositions which cure to solid form by heat treatment or otherwise. The word “solid” as used in the EP '407 publication and also herein means stable in shape and includes a gel or polymer network.
The inventions of the PCT '820 publication and the EP '407 publication were a significant breakthrough in the uniform dispersion of conductive particles and address the issue of particle aggregation and the consequences in fine pitch electronic interconnection [cf. U.S. Pat. No. 5,221,417 (Basanvanhally)]. However, the preparation of a curable particle-loaded ferrofluid adhesive composition compromises between the ferrofluid character of the composition, including high magnetization saturation and low viscosity at room temperature for rapid ordering of the particles, and the adhesive character of the composition, including the use of medium to high molecular weight systems having relatively high viscosity, to impart good mechanical properties and functionality to the cured adhesive.
U.S. patent application Ser. No. 09/143,879 filed Aug. 1, 1997 (“the '879 application”; now issued as U.S. Pat. No. 6,180,226) describes methods for producing monolayered random and ordered arrays of particles which are maintained in place by use of a cured tack layer. These methods employ a curable matrix in which the particles are dispersed and the curable matrix is partially cured to form a thin film which maintains the particles in place but does not substantially encase the particles. The methods of the '879 application are also described in U.S. patent application Ser. No. 10/059,435 filed Jan. 31, 2002 (“the '435 application”), which contains Examples 1-27 and FIGS. 1-11(b) of the '879 application. The '435 application describes a further example of the methods of the '879 application for producing monolayered random and ordered arrays of particles in patterns such as in discrete regions on a substrate.
It would be desirable to provide ways in which monolayers, including patterned monolayers, of dispersed or ordered arrays of particles may be prepared as well as films prepared therefrom which are easy, fast and employ readily available, easy to manufacture components and which allow for the reuseability/recovery of materials such as in particular expensive and/or government-regulated materials.
It would be particularly desirable to provide a method for forming monolayers of dispersed or ordered arrays of particles and films containing the arrays which allows for the recovery of unused or unuseable (e.g., in the end-use application of the array) materials such as the particles forming the array for example gold microparticles. The materials employed and in particular the particles used can be relatively expensive and accordingly it would be desirable to provide a method whereby unnecessary waste of such expensive materials and additional recovery costs of the materials is at least reduced, is desirably minimised and ideally avoided.
It would also be desirable to prepare stable monolayers, including patterned monolayers, of particles and arrays of particles and films prepared therefrom which are free or substantially free of ferromagnetic particles and which contain random and ordered arrays of particles with improved physical and performance characteristics, e.g., improved strength and/or adhesiveness as well as transparency or translucency, and the like.
It would also be particularly desirable to produce a substrate such as a film having monolayered random or ordered arrays of particles, including particles arranged in a repeated pattern, for example, repeated geometric shapes such as circular, square, or rectangular arrays of particles.
The '879 application and the '435 application [particularly Example 9 and FIGS. 11(a) and (b) in both applications] describe the application of a particle-containing ferrofluid adhesive formulation to a substrate and the placing of a second substrate over the top of the ferrofluid film. The assembled film is then compressed. Not only does the compression aim to achieve a substantially uniform fluid film, but pressure is applied which produces a fluid layer between the substrates such that the liquid layer is less than two particle diameters in thickness. This situation is referred to as a monolayer of particles.
In the '435 application, more particularly in Example 28, the compression apparatus for forming the monolayer is a laminating nip in which a plastic web (substrate) carrying the particle-loaded ferroadhesive mixture is brought together with another plastic web moving under identical tension and at the same speed. A confined monolayer of particles results due to the pressure of the laminating nip that brings the two webs together.
It is desirable to have a high density of separated substantive particles per unit area of the film. For this purpose, it is also desirable to use particles of small diameter, e.g., in the range from 2-6 micrometers, particularly 3-5 micrometers. However it has been found difficult to obtain a high density when compression is being used, particularly in a continuous lamination process, to achieve a substantially uniform fluid film between two substrates, prior to polymerization of the “tack layer”. In particular, when using the initial laminating nip described in the '435 application, it has been found that if the ferroadhesive is overloaded with particles, a build-up of substantive particles forms at the nip that subsequently causes uneven concentrations of particles on the web. For example, when the particles are spheres with a diameter of 5 micrometers, a 35% w/w concentration of particles in the ferroadhesive formulation can cause overloading of the laminating nip.
It is desirable to identify a method of forming a monolayer of particles with an increased density for a specific small particle as compared to that achieved hitherto and/or by use of a lower concentration of particles in the curable composition than was necessary to achieve a desired high density by methods used hitherto.
The '879 application and the '435 application both disclose that particles of two or more groups of different sizes but of substantially uniform size within the group of larger size may be used.